EP0436922A2 - Method and apparatus for treating effluent - Google Patents
Method and apparatus for treating effluent Download PDFInfo
- Publication number
- EP0436922A2 EP0436922A2 EP90125378A EP90125378A EP0436922A2 EP 0436922 A2 EP0436922 A2 EP 0436922A2 EP 90125378 A EP90125378 A EP 90125378A EP 90125378 A EP90125378 A EP 90125378A EP 0436922 A2 EP0436922 A2 EP 0436922A2
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- EP
- European Patent Office
- Prior art keywords
- waste water
- radiation source
- irradiation
- container
- line
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- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 238000000034 method Methods 0.000 title claims abstract description 37
- 239000007788 liquid Substances 0.000 claims abstract description 38
- 239000007800 oxidant agent Substances 0.000 claims abstract description 14
- 238000001556 precipitation Methods 0.000 claims abstract description 13
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 239000002351 wastewater Substances 0.000 claims description 114
- 230000005855 radiation Effects 0.000 claims description 75
- 238000011282 treatment Methods 0.000 claims description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- 238000003860 storage Methods 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- 239000000470 constituent Substances 0.000 claims description 6
- 239000000443 aerosol Substances 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052753 mercury Inorganic materials 0.000 abstract description 4
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 abstract description 3
- 230000001590 oxidative effect Effects 0.000 abstract description 2
- 230000001678 irradiating effect Effects 0.000 abstract 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical group N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 3
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000008139 complexing agent Substances 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 125000002015 acyclic group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 230000009969 flowable effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N hydrofluoric acid Substances F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- QPJSUIGXIBEQAC-UHFFFAOYSA-N n-(2,4-dichloro-5-propan-2-yloxyphenyl)acetamide Chemical compound CC(C)OC1=CC(NC(C)=O)=C(Cl)C=C1Cl QPJSUIGXIBEQAC-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 238000011369 optimal treatment Methods 0.000 description 1
- 125000005385 peroxodisulfate group Chemical group 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229940095064 tartrate Drugs 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
- C02F1/325—Irradiation devices or lamp constructions
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
- C02F2101/18—Cyanides
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/303—Complexing agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
Definitions
- the invention relates to a process for the treatment of wastewater which contains constituents which are difficult to degrade, in particular those which are difficult to oxidize.
- Wastewater often contains complexing agents that can form stable complexes with the metals contained in the wastewater.
- cyanide forms very stable complexes with various metals that cannot be completely broken down with conventional oxidizing agents.
- organic complexing agents such as EDTA, NTA, tartrate, form stable complexes with metals.
- Cyclic, acyclic or aromatic hydrocarbons and chlorinated hydrocarbons (CHC) contained in the wastewater can also only be removed from the wastewater with great expenditure on equipment.
- the poorly biodegradable constituents of the wastewater also include dye molecules and surfactants.
- Chlorine-containing chemicals such as. Are usually used for the treatment of industrial waste water for example, sodium bleaching liquor used. These substances have strong oxidizing properties and their use is therefore associated with disadvantages.
- the object of the invention is to provide a method for treating wastewater in which components of the wastewater that are difficult to degrade are removed reliably and without undesirable side effects.
- This object is achieved by a process in which the waste water is irradiated at least once with UV light from a UV radiation source in at least one process step.
- ozone is formed in small amounts by the irradiation with UV light, which oxidizes or splits the components of the wastewater that are difficult to decompose.
- the radiation is carried out with a radiation source which has a broad spectrum in the ultraviolet wavelength range.
- the wavelength range of the radiation source can be between 160 and below 400 nm and therein preferably between 240 and 370 nm lie. It is expedient if at least one high-pressure mercury lamp is used as the radiation source. This can be tubular and can be enclosed by a quartz glass jacket. The power of the lamp can preferably be between 0.5 and 20 kW. Depending on the prevailing conditions, it may be expedient if the wastewater is irradiated several times in succession with UV light and / or if it is irradiated by several UV radiation sources during the process. In this way, a longer residence time of the wastewater is achieved in the environment irradiated by the UV radiation source.
- the process according to the invention is suitable for the purification of waste water which contain constituents which are difficult to decompose, in particular those which are difficult to oxidize.
- it is suitable for the purification of waste water that arises during the treatment of metal surfaces, such as during electroplating.
- Further preferred fields of application of the method according to the invention are in the purification of waste water from the textile industry (e.g. dyeing works), printing press waste water (for example production of cardboard prints) and waste water from degreasing and oil removal systems.
- wastewater containing PCB and PCP and their descendants can also be treated with the method according to the invention, with a splitting of the substances mentioned being achieved.
- the irradiation is carried out in the presence of an oxidizing agent, the oxidizing agent being added to the waste water in particular before the irradiation.
- an oxidizing agent such as peroxodisulfates (eg potassium peroxodisulfate) can be added as the oxidizing agent. It is particularly advantageous if hydrogen peroxide is used as the oxidizing agent. In this case, the addition of the oxidizing agent means that no other substances are added to the Wastewater introduced, which could possibly lead to residues.
- the layer thickness with which the waste water is irradiated is preferably between 0.1 and 50 mm, in particular between 1.0 and 20 mm.
- the wastewater is preferably drawn thinly before and / or during the irradiation using rollers.
- the waste water is irradiated in liquid form, in particular in the form of a liquid under pressure.
- the overpressure can be between 0.1 and 3.5 bar.
- the wastewater is irradiated in intervals for a certain period of time. It is also preferably possible to atomize the waste water before or during the irradiation. In this way, the wastewater is irradiated in the form of an aerosol. Irradiation of flowing wastewater is preferred.
- a pretreatment in particular in a precipitation and / or filtration stage, is carried out before the waste water is irradiated.
- a precipitation step a so-called hydroxide precipitation can be carried out, in which metals are precipitated in the form of their hydroxides.
- a filtration on a suitable filter such as a sand filter can be carried out in a filtration stage.
- the wastewater is to be irradiated, for example in the form of an aerosol, or if the oxidation is to be increased by increasing the concentration of the ozone formed during the irradiation, it is advantageous if the wastewater is saturated with air and / or atomized before the irradiation. Possibly. it can also be advantageous if after-treatment of the wastewater is carried out, in particular in a precipitation stage. This has the advantage that the metal ions released, for example, when the stable complexes are broken down are removed from the waste water.
- ultrafiltration can be carried out first, then the irradiation by a UV radiation source and a subsequent precipitation reaction, an oxidizing agent possibly being added before the irradiation.
- the wastewater for irradiation is led around at least one, preferably tubular, UV radiation source, in particular helically.
- the method itself, but in particular the method step of irradiation with UV light can be carried out as a cycle process.
- the invention also relates to a device for treating wastewater with UV light, which is particularly suitable for carrying out the method according to the invention and in which at least one UV radiation source is surrounded for irradiation with at least one, preferably flowable, space for receiving wastewater.
- the UV radiation source is preferred placed in a flow-through container, in particular immersed in the waste water.
- one or more UV radiation sources can be immersed in the waste water in a container in which the waste water is located, or one or more radiation sources can be introduced into the walls or the bottom of the container by means of suitable devices, in order in this way to achieve one to achieve the most uniform possible irradiation of the wastewater.
- a preferred embodiment of the device according to the invention is present if at least one liquid line or at least one liquid space is arranged around at least one UV radiation source in such a way that all parts of the waste water volume are irradiated with substantially the same light energy during the irradiation.
- the device according to the invention is particularly characterized in that the UV radiation source is tubular.
- the UV radiation source has a quartz glass jacket. This quartz glass jacket is permeable to UV light, temperature stable and resistant to aggressive chemicals such as hydrofluoric or phosphoric acid.
- the temperature of the wastewater can increase during the irradiation, depending on the process conditions chosen, for example, temperatures of up to 100 ° C can be reached.
- cooling or heating of the wastewater before or during the irradiation may be expedient.
- it can be designed in such a way that air or water cooling is possible. Possibly.
- the radiation source can also be designed so that it can be flushed with inert gas. Cooling by the waste water can also be preferred.
- the radiation source can continue be designed as a helix, for example meandering. This is particularly expedient if wastewater surfaces are to be irradiated, for example during treatment with rollers.
- the device has at least one liquid line, it is advantageous if a plurality of liquid lines are arranged in the longitudinal direction parallel to the radiation source.
- at least one liquid line is arranged in such a way that it is placed in the form of a coiled tube with turns lying closely together in the longitudinal direction around the radiation source.
- the liquid line is designed as at least one, preferably coaxial sleeve around the radiation source. The embodiments mentioned make it possible in a particularly good manner that all parts of the waste water volume are irradiated with essentially the same light energy during the irradiation.
- a plurality of radiation sources in particular in the form of a ring, can preferably be arranged around a liquid line (“central tube”) through which the waste water is guided.
- the liquid line can be tortuous, for example helically shaped, in order to achieve the irradiation of the largest possible volume of waste water.
- the liquid line can also be in the form of an overflow pipe, the waste water being irradiated both when flowing through the pipe interior and after flowing out of the overflow in the form of a thin liquid film flowing down the outside of the pipe.
- a device according to the invention which has at least one liquid line, can expediently also be designed as a tube bundle, with several radiation sources and several Liquid lines are arranged alternately essentially parallel to one another. If one considers the cross-sectional area of such a tube bundle, radiation sources and liquid lines are arranged side by side in both transverse dimensions in such a way that the best possible use of space or area is given and a liquid line is irradiated by as many radiation sources as possible at the same time. If the radiation sources and liquid lines are arranged next to and above one another, for example in parallel rows, each liquid line is surrounded by at least four radiation sources when the rows are offset, and vice versa.
- the device can be designed so that the liquid lines are flowed through in only one direction or that the liquid lines are alternately guided in countercurrent to the radiation source.
- Radiation sources lying next to one another can also be arranged in such a way that the waste water can be guided transversely between them and around them.
- the volume enclosed by the liquid line or the liquid lines around the radiation source can have a layer thickness, in particular a radial layer thickness between 0.1 and 50 mm, in particular 1.0 and 20 mm.
- the radiation source in particular the quartz glass jacket, is adapted to the medium to be treated in terms of length and, if necessary, outer diameter.
- the dimensions of the radiation source or, in particular, of its quartz glass jacket in the longitudinal direction are expediently between 0.1 to 3 m, in particular 1.5 to 2.5 m. If it is a tubular radiation source, it has an outer diameter of 20 to 50 cm, in particular 30 to 40 cm.
- a high-pressure mercury lamp is provided as the radiation source.
- the device can be advantageous to surround the device with a jacket tube made of reflective material such as stainless steel, which is optionally polished. In this way the light energy with which the wastewater is irradiated is increased.
- the device according to the invention is characterized in that the at least one UV radiation source is arranged between a first container, in particular a storage container, and a second container, in particular a collecting container, the first container with the UV radiation source and this are connected to the second container via suitable connecting lines, there is a supply line for supplying the waste water on the first container and a discharge line for discharging the water on the second container and a feed pump and possibly at least one flow meter and at least one valve or Slides for determining and regulating the flow rate are arranged.
- at least one connection for the supply of further substances, in particular an oxidizing agent can be provided on the supply line, the first container and / or the connecting line.
- the substance in question can be added to the wastewater before irradiation.
- the feed line is connected to a precipitation and / or filtering device and the discharge line is connected to a precipitation device.
- the device can be characterized in that the discharge line on the second container is designed as a return line or there is an additional return line on the second container. The return line is provided for returning the waste water into the first container and / or into the connecting lines. This feature enables feedback of the wastewater and thus to enable a circular process.
- the connecting line between the first container and the UV radiation source is additionally connected to the first container via a further connecting line. In this way, excess wastewater can possibly be returned to the first tank.
- a UV radiation source 3 is arranged between a liquid storage container 1 for waste water and a collecting container 2, the storage container 1 being provided with an agitator 4.
- the reservoir 1 is connected to the radiation source 3 via a connecting line 5, in the course of which there is a liquid pump 6 for conveying the waste water, a flow meter 7 and two slides 8 and 9 for regulating the flow rate.
- the radiation source 3 is connected to the collecting container 2 via a connecting line 10, from which a drain line 11 branches off, which is provided with a slide 12 at the end.
- the connecting line 5 is via a further connecting line 13 additionally connected to the storage container 1, so that a return of the waste water from the connecting line 5 to the storage container 1 is made possible. To open or close the connecting line 13, this has a slide 14.
- the feed line 15 On the reservoir 1 there is a feed line 15 through which the waste water is introduced into the reservoir 1.
- the feed line 15 has a connection 16 through which the supply of an oxidizing agent is possible.
- the collecting container 2 has a discharge line 17 provided with a slide 18, through which the waste water can be drained from the collecting container 2 or can be introduced into the storage container or into one of the connecting lines to form a cycle.
- FIG. 2 schematically shows a quartz burner 3 with an outer diameter of 40 mm and a length of 150 mm as UV radiation source, which is surrounded by a liquid line 19 in the form of a tube coil 20.
- the liquid line 19 consists of quartz glass, the individual windings 21 of which lie close together and are wound around the radiation source 3 at a small pitch angle.
- the inner diameter of the line 19 can be 5, 10 or 15 mm, depending on the type of liquid to be treated.
- the tube coil 20 can be arranged closely around the radiation source. An intermediate space for a cooling medium can also be provided.
- the burner has an output of 1.5 kW and can be increased by using longer burners.
- a method according to the invention is carried out with the device shown in FIG.
- the wastewater is over the feed line is introduced into the storage container 1 and mixed well with the aid of the agitator 4.
- the UV radiation source is then put into operation and the waste water is guided past the radiation source 3 by means of the pump 6 through the connecting line 5.
- a liquid line 19, which is arranged around the radiation source 3 in the manner shown in FIG. 2, can be used, for example, to bypass the waste water.
- the volume of waste water which is directed past the radiation source 3 is adjusted with the aid of the flow meter 7 and the slide 8 and 9. Any additional output of the feed pump 6 that may occur is fed back into the storage container 1 via the connecting line 13 and by actuating the slide 14.
- the waste water used in Example 1 contained cyanide and had an initial concentration of cyanide of 20 mg CN / 1 waste water.
- the wastewater was adjusted to a pH value of ⁇ 10 in order to avoid the escape of hydrocyanic acid. This wastewater was directed past the UV radiation source at different flow rates and after a single exposure the cyanide concentration in the treated wastewater was measured. The results shown in the following table were obtained:
- Example 2 was carried out as in Example 1. Wastewater was used as wastewater that has an EDTA concentration of 70 mg EDTA / l wastewater. In addition, 16 hydrogen peroxide in a concentration of 1 l of 30% H2O2 per 100 l of wastewater was added to the wastewater. After one exposure, the results shown in the following table were obtained.
- the optimal flow rate for the device used is less than approx. 200 l / h.
- Example 3 is carried out as example 2. A waste water containing 90 mg methylene chloride / l waste water is used as waste water. The same amount of hydrogen peroxide as used in Example 2 was added to port 16 via port 16. The following results were obtained:
- the chlorinated hydrocarbon used in this example also shows that very good treatment results can be obtained if the flow rates are not too high.
- the concentration of constituents of the waste water which are difficult to degrade can be significantly reduced even with irradiation. If the treatment in one irradiation step is not sufficient, it is easily possible to carry out the irradiation several times in succession or to connect several UV radiation sources in series and to guide the waste water past it. In this way, the residence time of the waste water at the radiation source is increased.
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- Hydrology & Water Resources (AREA)
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- Environmental & Geological Engineering (AREA)
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Abstract
Description
Die Erfindung betrifft ein Verfahren zur Behandlung von Abwasser, welches schwer abbaubare, insbesondere schwer oxidierbare Bestandteile enthält.The invention relates to a process for the treatment of wastewater which contains constituents which are difficult to degrade, in particular those which are difficult to oxidize.
Abwässer enthalten oft Komplexbildner, die mit den im Abwasser enthaltenen Metallen stabile Komplexe bilden können. So bildet beispielsweise Cyanid mit verschiedenen Metallen sehr stabile Komplexe, die mit herkömmlichen Oxidationsmitteln nur unvollständig abgebaut werden können. In gleicher Weise bilden organische Komplexbildner, wie beispielsweise EDTA, NTA, Tartrat, mit Metallen stabile Komplexe. Im Abwasser enthaltene cyclische, acyclische oder aromatische Kohlenwasserstoffe und chlorierte Kohlenwasserstoffe (CKW) können ebenfalls nur mit hohem apparativem Aufwand aus dem Abwasser entfernt werden. Unter die schwer abbaubaren Bestandteile des Abwassers fallen unter anderem auch Farbstoffmoleküle und Tenside. Üblicherweise werden für die Behandlung industrieller Abwässer chlorhaltige Chemikalien, wie beispielsweise Natronbleichlauge, verwendet. Diese Stoffe besitzen stark oxidierende Eigenschaften, und ihre Verwendung ist deshalb mit Nachteilen verbunden. Bei der Oxidation des Abwassers werden nämlich unter anderem auch im Abwasser enthaltene organische Stoffgruppen chloriert. Damit erhöht sich der Anteil der organischen Halogenide im Abwasser, und ein Grenzwert für den sogenannten AOX (Absorbierbare organische Halogenide)-Wert kann unter Umständen nicht eingehalten werden.Wastewater often contains complexing agents that can form stable complexes with the metals contained in the wastewater. For example, cyanide forms very stable complexes with various metals that cannot be completely broken down with conventional oxidizing agents. In the same way, organic complexing agents, such as EDTA, NTA, tartrate, form stable complexes with metals. Cyclic, acyclic or aromatic hydrocarbons and chlorinated hydrocarbons (CHC) contained in the wastewater can also only be removed from the wastewater with great expenditure on equipment. The poorly biodegradable constituents of the wastewater also include dye molecules and surfactants. Chlorine-containing chemicals such as. Are usually used for the treatment of industrial waste water for example, sodium bleaching liquor used. These substances have strong oxidizing properties and their use is therefore associated with disadvantages. During the oxidation of the wastewater, organic substance groups contained in the wastewater are chlorinated. This increases the proportion of organic halides in the wastewater, and a limit value for the so-called AOX (absorbable organic halide) value may not be met under certain circumstances.
Die Erfindung stellt sich die Aufgabe, ein Verfahren zur Abwasserbehandlung zur Verfügung zu stellen, bei dem schwer abbaubare Bestandteile des Abwassers zuverlässig und ohne unerwünschte Nebenwirkungen entfernt werden.The object of the invention is to provide a method for treating wastewater in which components of the wastewater that are difficult to degrade are removed reliably and without undesirable side effects.
Gelöst wird diese Aufgabe durch ein Verfahren, bei dem das Abwasser in mindestens einem Verfahrensschritt mindestens einmal mit UV-Licht einer UV-Strahlungsquelle bestrahlt wird.This object is achieved by a process in which the waste water is irradiated at least once with UV light from a UV radiation source in at least one process step.
Durch die Bestrahlung mit UV-Licht kann das Abwasser mit relativ geringem Aufwand gereinigt werden, und die bisher nötigen aufwendigen Apparaturen zur Abwasserreinigung können eingespart werden. Auch eine ggf. nötige Entsorgung der im Abwasser enthaltenen schwer abbaubaren Bestandteile als Sondermüll kann vermieden werden. Bei dem erfindungsgemäßen Verfahren wird durch die Bestrahlung mit UV-Licht in geringen Mengen Ozon gebildet, das die schwer abbaubaren Bestandteile des Abwassers oxidiert bzw. spaltet. Durch das Erzeugen des Ozons in situ kann das direkte gefährliche Arbeiten mit Ozon vermieden werden, und auch die mit dem Einsatz von chlorhaltigen Oxidationsmitteln verbundenen Nachteile treten nicht auf. Es ist vorteilhaft, wenn die Bestrahlung mit einer Strahlungsquelle durchgeführt wird, die ein breites Spektrum im ultravioletten Wellenlängenbereich besitzt. Dabei kann der Wellenlängenbereich der Strahlungsquelle zwischen 160 und unter 400 nm und darin bevorzugt zwischen 240 und 370 nm liegen. Es ist zweckmäßig, wenn als Strahlungsquelle mindestens eine Quecksilber-Hochdrucklampe verwendet wird. Diese kann dabei rohrförmig ausgebildet und von einem Quarzglasmantel umschlossen sein. Bevorzugt kann die Leistung der Lampe zwischen 0,5 und 20 kW betragen. Je nach den vorliegenden Verhältnissen kann es zweckmäßig sein, wenn das Abwasser mehrere Male hintereinander mit UV-Licht bestrahlt wird und/oder wenn es während des Verfahrens von mehreren UV-Strahlungsquellen bestrahlt wird. Auf diese Weise wird eine höhere Verweilzeit des Abwassers in der von der UV-Strahlungsquelle bestrahlten Umgebung erreicht.By irradiation with UV light, the wastewater can be cleaned with relatively little effort, and the previously required complex equipment for wastewater treatment can be saved. Any necessary disposal of the difficultly degradable constituents contained in the waste water as special waste can also be avoided. In the method according to the invention, ozone is formed in small amounts by the irradiation with UV light, which oxidizes or splits the components of the wastewater that are difficult to decompose. By generating the ozone in situ, the direct dangerous work with ozone can be avoided, and the disadvantages associated with the use of chlorine-containing oxidizing agents also do not occur. It is advantageous if the radiation is carried out with a radiation source which has a broad spectrum in the ultraviolet wavelength range. The wavelength range of the radiation source can be between 160 and below 400 nm and therein preferably between 240 and 370 nm lie. It is expedient if at least one high-pressure mercury lamp is used as the radiation source. This can be tubular and can be enclosed by a quartz glass jacket. The power of the lamp can preferably be between 0.5 and 20 kW. Depending on the prevailing conditions, it may be expedient if the wastewater is irradiated several times in succession with UV light and / or if it is irradiated by several UV radiation sources during the process. In this way, a longer residence time of the wastewater is achieved in the environment irradiated by the UV radiation source.
Das erfindungsgemäße Verfahren ist zur Reinigung von Abwässern geeignet, die schwer abbaubare, insbesondere schwer oxidierbare Bestandteile enthalten. Insbesondere ist es zur Reinigung von Abwässern geeignet, die bei der Behandlung von Metalloberflächen wie beispielsweise beim Galvanisieren entstehen. Weitere bevorzugte Anwendungsgebiete des erfindungsgemäßen Verfahrens liegen bei der Reinigung von Abwässern aus der Textilindustrie (z.B. Färbereien), von Druckereiabwässern (beispielsweise Herstellung von Kartonage-Drucken) und von Abwässern aus Entfettungs- und Entölungsanlagen. Insbesondere können auch Abwässer, die PCB und PCP sowie deren Abkömmlinge enthalten, mit dem erfindungsgemäßen Verfahren behandelt werden, wobei eine Spaltung der genannten Stoffe erreicht wird.The process according to the invention is suitable for the purification of waste water which contain constituents which are difficult to decompose, in particular those which are difficult to oxidize. In particular, it is suitable for the purification of waste water that arises during the treatment of metal surfaces, such as during electroplating. Further preferred fields of application of the method according to the invention are in the purification of waste water from the textile industry (e.g. dyeing works), printing press waste water (for example production of cardboard prints) and waste water from degreasing and oil removal systems. In particular, wastewater containing PCB and PCP and their descendants can also be treated with the method according to the invention, with a splitting of the substances mentioned being achieved.
Nach einer bevorzugten Ausführungsform des erfindungsgemäßen Verfahrens wird die Bestrahlung in Gegenwart eines Oxidationsmittels durchgeführt, wobei das Oxidationsmittel dem Abwasser insbesondere vor der Bestrahlung zugegeben wird. Als Oxidationsmittel können übliche, vorzugsweise chlorfreie Oxidationsmittel wie Peroxodisulfate (z.B. Kaliumperoxodisulfat) zugegeben werden. Besonders vorteilhaft ist es, wenn als Oxidationsmittel Wasserstoffperoxid verwendet wird. In diesem Fall werden durch die Zugabe des Oxidationsmittels keine weiteren Stoffe in das Abwasser eingebracht, die eventuell zu Rückständen führen könnten.According to a preferred embodiment of the method according to the invention, the irradiation is carried out in the presence of an oxidizing agent, the oxidizing agent being added to the waste water in particular before the irradiation. Customary, preferably chlorine-free, oxidizing agents such as peroxodisulfates (eg potassium peroxodisulfate) can be added as the oxidizing agent. It is particularly advantageous if hydrogen peroxide is used as the oxidizing agent. In this case, the addition of the oxidizing agent means that no other substances are added to the Wastewater introduced, which could possibly lead to residues.
Es ist vorteilhaft, während der Bestrahlung alle Teile des Abwasservolumens mit im wesentlichen der gleichen Lichtenergie bzw. Lichtmenge zu bestrahlen. Dies kann dadurch erreicht werden, daß der Abstand zwischen der mindestens einen UV-Strahlungsquelle und dem bestrahlten Medium an allen Stellen im wesentlichen gleichmäßig ist, damit das gesamte Abwasser der gleichen Behandlung unterworfen wird. Bevorzugt beträgt die Schichtdicke, mit der das Abwasser bestrahlt wird, zwischen 0,1 und 50 mm, insbesondere zwischen 1,0 und 20 mm. Vorzugsweise wird das Abwasser vor und/oder während der Bestrahlung über Walzen dünngezogen.It is advantageous to irradiate all parts of the waste water volume with essentially the same light energy or quantity of light during the irradiation. This can be achieved in that the distance between the at least one UV radiation source and the irradiated medium is essentially uniform at all points, so that the entire wastewater is subjected to the same treatment. The layer thickness with which the waste water is irradiated is preferably between 0.1 and 50 mm, in particular between 1.0 and 20 mm. The wastewater is preferably drawn thinly before and / or during the irradiation using rollers.
Es ist zweckmäßig, wenn das Abwasser in flüssiger Form, insbesondere in Form einer unter Druck stehenden Flüssigkeit bestrahlt wird. Dabei kann der Überdruck zwischen 0,1 und 3,5 bar betragen. In bestimmten Fällen ist es auch möglich, die Bestrahlung mit einer ruhenden insbesondere drucklosen Flüssigkeit vorzunehmen. In einem solchen Fall wird das Abwasser in Intervallen nacheinander für einen bestimmten Zeitraum bestrahlt. Vorzugsweise ist es auch möglich, das Abwasser vor oder während der Bestrahlung zu vernebeln. Auf diese Weise wird das Abwasser in Form eines Aerosols bestrahlt. Eine Bestrahlung von strömendem Abwasser ist jedoch bevorzugt.It is expedient if the waste water is irradiated in liquid form, in particular in the form of a liquid under pressure. The overpressure can be between 0.1 and 3.5 bar. In certain cases it is also possible to carry out the irradiation with a dormant, in particular unpressurized, liquid. In such a case, the wastewater is irradiated in intervals for a certain period of time. It is also preferably possible to atomize the waste water before or during the irradiation. In this way, the wastewater is irradiated in the form of an aerosol. Irradiation of flowing wastewater is preferred.
Nach einer bevorzugten Ausführungsform der Erfindung wird vor der Bestrahlung des Abwassers eine Vorbehandlung, insbesondere in einer Fällungs- und/oder Filtrationsstufe durchgeführt. Dies kann dann zu Vorteilen führen, wenn eine ggf. vorhandene Trübung des Abwassers bzw. eine hohe Salzkonzentration im Abwasser die UV-Strahlen zu stark absorbieren und damit die Effektivität des erfindungsgemäßen Verfahrens beeinträchtigen würde. So kann beispielsweise in einer Fällungsstufe eine sogenannte Hydroxid-fällung durchgeführt werden, bei der Metalle in Form ihrer Hydroxide ausgefällt werden. Alternativ oder zusätzlich kann in einer Filtrationsstufe eine Filtration an einem geeigneten Filter wie beispielsweise einem Sandfilter vorgenommen werden. Soll die Bestrahlung des Abwassers beispielsweise in Form eines Aerosols durchgeführt werden oder soll die Oxidation durch eine Konzentrationserhöhung des bei der Bestrahlung entstehenden Ozons gesteigert werden, ist es vorteilhaft, wenn das Abwasser vor der Bestrahlung mit Luft gesättigt und/oder zerstäubt wird. Ggf. kann es auch vorteilhaft sein, wenn nach der Bestrahlung eine Nachbehandlung des Abwassers, insbesondere in einer Fällungsstufe durchgeführt wird. Dies hat den Vorteil, daß die beispielsweise beim Abbau der stabilen Komplexe frei werdenden Metallionen aus dem Abwasser entfernt werden. So kann bei der Reinigung von Abwässern, insbesondere solchen, die bei der Kartonage-Druckerei entstehen, zuerst eine Ultrafiltration, dann die Bestrahlung durch eine UV-Strahlungsquelle und eine anschließende Fällungsreaktion durchgeführt werden, wobei vor der Bestrahlung ggf. ein Oxidationsmittel zugegeben wird.According to a preferred embodiment of the invention, a pretreatment, in particular in a precipitation and / or filtration stage, is carried out before the waste water is irradiated. This can lead to advantages if a possible turbidity of the waste water or a high salt concentration in the waste water absorbs the UV rays too strongly and would thus impair the effectiveness of the method according to the invention. So can For example, in a precipitation step, a so-called hydroxide precipitation can be carried out, in which metals are precipitated in the form of their hydroxides. Alternatively or additionally, a filtration on a suitable filter such as a sand filter can be carried out in a filtration stage. If the wastewater is to be irradiated, for example in the form of an aerosol, or if the oxidation is to be increased by increasing the concentration of the ozone formed during the irradiation, it is advantageous if the wastewater is saturated with air and / or atomized before the irradiation. Possibly. it can also be advantageous if after-treatment of the wastewater is carried out, in particular in a precipitation stage. This has the advantage that the metal ions released, for example, when the stable complexes are broken down are removed from the waste water. In the treatment of waste water, in particular that which arises at the cardboard box printing plant, ultrafiltration can be carried out first, then the irradiation by a UV radiation source and a subsequent precipitation reaction, an oxidizing agent possibly being added before the irradiation.
Es ist beim erfindungsgemäßen Verfahren bevorzugt, wenn das Abwasser zur Bestrahlung um mindestens eine, vorzugsweise rohrförmige UV-Strahlungsquelle geführt wird, insbesondere wendelförmig. Beim erfindungsgemäßen Verfahren kann das Verfahren selbst, insbesondere aber der Verfahrensschritt der Bestrahlung mit UV-Licht als Kreislaufprozeß durchgeführt werden.In the method according to the invention, it is preferred if the wastewater for irradiation is led around at least one, preferably tubular, UV radiation source, in particular helically. In the method according to the invention, the method itself, but in particular the method step of irradiation with UV light, can be carried out as a cycle process.
Die Erfindung betrifft ebenfalls eine Vorrichtung zur Behandlung von Abwasser mit UV-Licht, die insbesondere zur Durchführung des erfindungsgemäßen Verfahrens geeignet ist und bei der zur Bestrahlung mindestens eine UV-Strahlungsquelle mit mindestens einem, vorzugsweise durchströmbaren, Raum zur Aufnahme von Abwasser umgeben ist. Dabei ist die UV-Strahlungsquelle bevorzugt in einen durchströmbaren Behälter gesetzt, insbesondere in das Abwasser eingetaucht. So können in einen Behälter, in dem sich das Abwasser befindet, eine oder mehrere UV-Strahlungsquellen in das Abwasser eingetaucht werden oder es können über geeignete Vorrichtungen in den Wänden oder dem Boden des Behälters eine oder mehrere Strahlungsquellen eingebracht sein, um auf diese Weise eine möglichst gleichmäßige Bestrahlung des Abwassers zu erreichen.The invention also relates to a device for treating wastewater with UV light, which is particularly suitable for carrying out the method according to the invention and in which at least one UV radiation source is surrounded for irradiation with at least one, preferably flowable, space for receiving wastewater. The UV radiation source is preferred placed in a flow-through container, in particular immersed in the waste water. Thus, one or more UV radiation sources can be immersed in the waste water in a container in which the waste water is located, or one or more radiation sources can be introduced into the walls or the bottom of the container by means of suitable devices, in order in this way to achieve one to achieve the most uniform possible irradiation of the wastewater.
Eine bevorzugte Ausführungsform der erfindungsgemäßen Vorrichtung liegt dann vor, wenn um mindestens eine UV-Strahlungsquelle mindestens eine Flüssigkeitsleitung oder mindestens ein Flüssigkeitsraum so angeordnet ist, daß alle Teile des Abwasservolumens während der Bestrahlung mit im wesentlichen der gleichen Lichtenergie bestrahlt werden.A preferred embodiment of the device according to the invention is present if at least one liquid line or at least one liquid space is arranged around at least one UV radiation source in such a way that all parts of the waste water volume are irradiated with substantially the same light energy during the irradiation.
Die erfindungsgemäße Vorrichtung ist insbesondere dadurch gekennzeichnet, daß die UV-Strahlungsquelle rohrförmig ausgebildet ist. In Weiterbildung ist es bevorzugt, wenn die UV-Strahlungsquelle einen Quarzglasmantel aufweist. Dieser Quarzglasmantel ist für UV-Licht durchlässig, temperaturstabil sowie beständig gegen aggressive Chemikalien wie beispielsweise Fluß- oder Phosphorsäure. Während der Bestrahlung kann sich die Temperatur des Abwassers erhöhen, wobei je nach den gewählten Verfahrensbedingungen beispielsweise Temperaturen von bis zu 100°C erreicht werden können. Je nachdem, mit welcher Temperatur das Abwasser in der Praxis in den Verfahrensschritt der UV-Bestrahlung eintritt, kann eine Abkühlung oder Aufheizung des Abwassers vor oder während der Bestrahlung zweckmäßig sein. Zur Kühlung der Strahlungsquelle während des Betriebs kann diese so ausgestaltet sein, daß eine Luft- oder Wasserkühlung möglich ist. Ggf. kann die Strahlungsquelle auch so ausgebildet sein, daß sie mit Inertgas gespült werden kann. Auch eine Kühlung durch das Abwasser kann bevorzugt sein. Die Strahlungsquelle kann weiterhin als Wendel, beispielsweise mäanderförmig ausgebildet sein. Dies ist insbesondere dann zweckmäßig, wenn Abwasserflächen wie beispielsweise bei einer Behandlung mit Walzen bestrahlt werden sollen.The device according to the invention is particularly characterized in that the UV radiation source is tubular. In a further development, it is preferred if the UV radiation source has a quartz glass jacket. This quartz glass jacket is permeable to UV light, temperature stable and resistant to aggressive chemicals such as hydrofluoric or phosphoric acid. The temperature of the wastewater can increase during the irradiation, depending on the process conditions chosen, for example, temperatures of up to 100 ° C can be reached. Depending on the temperature at which the wastewater enters the UV irradiation process step in practice, cooling or heating of the wastewater before or during the irradiation may be expedient. To cool the radiation source during operation, it can be designed in such a way that air or water cooling is possible. Possibly. the radiation source can also be designed so that it can be flushed with inert gas. Cooling by the waste water can also be preferred. The radiation source can continue be designed as a helix, for example meandering. This is particularly expedient if wastewater surfaces are to be irradiated, for example during treatment with rollers.
Weist die Vorrichtung mindestens eine Flüssigkeitsleitung auf, so ist es vorteilhaft, wenn mehrere Flüssigkeitsleitungen in Längsrichtung parallel um die Strahlungsquelle angeordnet sind. Nach einer weiteren bevorzugten Ausführungsform ist mindestens eine Flüssigkeitsleitung so angeordnet, daß sie in Form einer Rohrwendel mit dicht aneinander liegenden Windungen in Längsrichtung um die Strahlungsquelle gelegt ist. Insbesondere ist auch eine Ausführungsform bevorzugt, bei der die Flüssigkeitsleitung als mindestens eine, vorzugsweise koaxiale Hülse um die Strahlungsquelle ausgebildet ist. Die genannten Ausführungsformen ermöglichen es auf besonders gute Weise, daß alle Teile des Abwasservolumens während der Bestrahlung mit im wesentlichen der gleichen Lichtenergie bestrahlt werden.If the device has at least one liquid line, it is advantageous if a plurality of liquid lines are arranged in the longitudinal direction parallel to the radiation source. According to a further preferred embodiment, at least one liquid line is arranged in such a way that it is placed in the form of a coiled tube with turns lying closely together in the longitudinal direction around the radiation source. In particular, an embodiment is also preferred in which the liquid line is designed as at least one, preferably coaxial sleeve around the radiation source. The embodiments mentioned make it possible in a particularly good manner that all parts of the waste water volume are irradiated with essentially the same light energy during the irradiation.
Weiterhin können nach der Erfindung vorzugsweise mehrere Strahlungsquellen, insbesondere ringförmig, um eine Flüssigkeitsleitung ("Mittelrohr"), durch die das Abwasser geführt wird, angeordnet sein. Dabei kann die Flüssigkeitsleitung gewunden, beispielsweise wendelförmig ausgebildet sein, um die Bestrahlung eines möglichst großen Abwasservolumens zu erreichen. Die Flüssigkeitsleitung kann auch in Form eines Überlaufrohres vorliegen, wobei das Abwasser sowohl beim Durchströmen des Rohrinneren als auch nach dem Ausströmen aus dem Überlauf in Form eines dünnen, an der Außenseite des Rohres herabfließenden Flüssigkeitsfilmes bestrahlt wird.Furthermore, according to the invention, a plurality of radiation sources, in particular in the form of a ring, can preferably be arranged around a liquid line (“central tube”) through which the waste water is guided. In this case, the liquid line can be tortuous, for example helically shaped, in order to achieve the irradiation of the largest possible volume of waste water. The liquid line can also be in the form of an overflow pipe, the waste water being irradiated both when flowing through the pipe interior and after flowing out of the overflow in the form of a thin liquid film flowing down the outside of the pipe.
Eine erfindungsgemäße Vorrichtung, die mindestens eine Flüssigkeitsleitung aufweist, kann zweckmäßig auch als Rohrbündel ausgebildet sein, wobei mehrere Strahlungsquellen und mehrere Flüssigkeitsleitungen im wesentlichen parallel nebeneinander abwechselnd angeordnet sind. Betrachtet man die Querschnittsfläche eines solchen Rohrbündels, so sind in beiden Querdimensionen Strahlungsquellen und Flüssigkeitsleitungen so nebeneinander angeordnet, daß eine möglichst gute Raum- bzw. Flächenausnutzung gegeben ist und eine Flüssigkeitsleitung von möglichst vielen Strahlungsquellen gleichzeitig bestrahlt wird. Sind die Strahlungsquellen und Flüssigkeitsleitungen beispielsweise in parallelen Reihen neben- und übereinander angeordnet, so ist bei versetzter Anordnung der Reihen jede Flüssigkeitsleitung von mindestens vier Strahlungsquellen umgeben und umgekehrt. Die Vorrichtung kann dabei so ausgebildet sein, daß die Flüssigkeitsleitungen nur in einer Richtung durchströmt werden oder daß die Flüssigkeitsleitungen abwechselnd im Gegenstrom an der Strahlungsquelle vorbeigeführt werden. Es können auch parallel nebeneinander liegende Strahlungsquellen so angeordnet sein, daß das Abwasser in Querrichtung zwischen ihnen und um sie geführt werden kann.A device according to the invention, which has at least one liquid line, can expediently also be designed as a tube bundle, with several radiation sources and several Liquid lines are arranged alternately essentially parallel to one another. If one considers the cross-sectional area of such a tube bundle, radiation sources and liquid lines are arranged side by side in both transverse dimensions in such a way that the best possible use of space or area is given and a liquid line is irradiated by as many radiation sources as possible at the same time. If the radiation sources and liquid lines are arranged next to and above one another, for example in parallel rows, each liquid line is surrounded by at least four radiation sources when the rows are offset, and vice versa. The device can be designed so that the liquid lines are flowed through in only one direction or that the liquid lines are alternately guided in countercurrent to the radiation source. Radiation sources lying next to one another can also be arranged in such a way that the waste water can be guided transversely between them and around them.
Das von der Flüssigkeitsleitung bzw. den Flüssigkeitsleitungen um die Strahlungsquelle eingeschlossene Volumen kann eine Schichtdicke, insbesondere eine radiale Schichtdicke zwischen 0,1 und 50 mm, insbesondere 1,0 und 20 mm aufweisen. Die Strahlungsquelle, insbesondere der Quarzglasmantel ist in Länge und ggf. Außendurchmesser dem zu behandelnden Medium angepaßt. Dabei betragen die Abmessungen der Strahlungsquelle bzw. insbesondere ihres Quarzglasmantels in Längsrichtung zweckmäßig zwischen 0,1 bis 3 m, insbesondere 1,5 bis 2,5 m. Handelt es sich um eine rohrförmige Strahlungsquelle, so besitzt diese einen Außendurchmesser von 20 bis 50 cm, insbesondere 30 bis 40 cm. Als Strahlungsquelle ist insbesondere eine Quecksilber-Hochdrucklampe vorgesehen.The volume enclosed by the liquid line or the liquid lines around the radiation source can have a layer thickness, in particular a radial layer thickness between 0.1 and 50 mm, in particular 1.0 and 20 mm. The radiation source, in particular the quartz glass jacket, is adapted to the medium to be treated in terms of length and, if necessary, outer diameter. The dimensions of the radiation source or, in particular, of its quartz glass jacket in the longitudinal direction are expediently between 0.1 to 3 m, in particular 1.5 to 2.5 m. If it is a tubular radiation source, it has an outer diameter of 20 to 50 cm, in particular 30 to 40 cm. In particular, a high-pressure mercury lamp is provided as the radiation source.
Zur Verbesserung der Bestrahlung kann es vorteilhaft sein, die Vorrichtung mit einem Hüllenrohr aus reflektierendem Material wie beispielsweise Edelstahl, der ggf. poliert ist, zu umgeben. Auf diese Weise wird die Lichtenergie, mit der das Abwasser bestrahlt wird, erhöht.To improve the radiation, it can be advantageous to surround the device with a jacket tube made of reflective material such as stainless steel, which is optionally polished. In this way the light energy with which the wastewater is irradiated is increased.
In einer bevorzugten Ausführungsform ist die erfindungsgemäße Vorrichtung dadurch gekennzeichnet, daß die mindestens eine UV-Strahlungsquelle zwischen einem ersten Behälter, insbesondere einem Vorratsbehälter, und einem zweiten Behälter, insbesondere einem Auffangbehälter, angeordnet ist, wobei der erste Behälter mit der UV-Strahlungsquelle und diese mit dem zweiten Behälter über geeignete Verbindungsleitungen miteinander verbunden sind, sich am ersten Behälter eine Zuführleitung zur Zuleitung des Abwassers und am zweiten Behälter eine Abführleitung zur Ableitung des Wassers befinden und im Verlauf der Verbindungsleitungen eine Förderpumpe und ggf. mindestens ein Strömungsmesser und mindestens ein Ventil bzw. Schieber zur Bestimmung und Regulierung der Durchflußmenge angeordnet sind. Dabei kann insbesondere an der Zuführleitung, dem ersten Behälter und/oder der Verbindungsleitung mindestens ein Anschluß für die Zuleitung weiterer Stoffe, insbesondere eines Oxidationsmittels, vorgesehen sein. Dadurch kann der betreffende Stoff vor der Bestrahlung dem Abwasser zugegeben werden. In Weiterbildung ist die Zuführleitung mit einer Fällungs- und/oder Filtriereinrichtung bzw. die Abführleitung mit einer Fällungseinrichtung verbunden. Dadurch ist es möglich, das Abwasser vor bzw. nach der Bestrahlung einer weiteren Behandlung zu unterwerfen. In Weiterbildung kann die Vorrichtung dadurch gekennzeichnet sein, daß die Abführleitung am zweiten Behälter als Rückführleitung ausgebildet ist oder sich am zweiten Behälter zusätzlich eine Rückführleitung befindet. Dabei ist die Rückführleitung jeweils zur Rückführung des Abwassers in den ersten Behälter und/oder in die Verbindungsleitungen vorgesehen. Durch dieses Merkmal wird es möglich, eine Ruckführung des Abwassers und damit einen Kreislaufprozeß zu ermöglichen. Bei einer bevorzugten Vorrichtung ist es vorgesehen, daß die Verbindungsleitung zwischen dem ersten Behälter und der UV-Strahlunsquelle über eine weitere Verbindungsleitung zusätzlich mit dem ersten Behälter verbunden ist. Dadurch kann ggf. überschüssiges Abwasser in den ersten Behälter zurückgeleitet werden.In a preferred embodiment, the device according to the invention is characterized in that the at least one UV radiation source is arranged between a first container, in particular a storage container, and a second container, in particular a collecting container, the first container with the UV radiation source and this are connected to the second container via suitable connecting lines, there is a supply line for supplying the waste water on the first container and a discharge line for discharging the water on the second container and a feed pump and possibly at least one flow meter and at least one valve or Slides for determining and regulating the flow rate are arranged. In particular, at least one connection for the supply of further substances, in particular an oxidizing agent, can be provided on the supply line, the first container and / or the connecting line. As a result, the substance in question can be added to the wastewater before irradiation. In a further development, the feed line is connected to a precipitation and / or filtering device and the discharge line is connected to a precipitation device. This makes it possible to subject the wastewater to further treatment before or after irradiation. In a further development, the device can be characterized in that the discharge line on the second container is designed as a return line or there is an additional return line on the second container. The return line is provided for returning the waste water into the first container and / or into the connecting lines. This feature enables feedback of the wastewater and thus to enable a circular process. In a preferred device it is provided that the connecting line between the first container and the UV radiation source is additionally connected to the first container via a further connecting line. In this way, excess wastewater can possibly be returned to the first tank.
Die folgenden Beispiele zeigen bevorzugte Ausführungsformen der Erfindung. Dabei können die einzelnen Merkmale jeweils für sich alleine oder in Kombination miteinander bei einer Ausführungsform der Erfindung verwirklicht sein.The following examples show preferred embodiments of the invention. The individual features can be realized individually or in combination with one another in one embodiment of the invention.
- Fig. 1Fig. 1
- eine schematische Darstellung einer erfindungsgemäßen Vorrichtung is a schematic representation of a device according to the invention
- Fig. 2Fig. 2
- eine Darstellung einer UV-Strahlungsquelle nach der Erfindung, die von einer Flüssigkeitsleitung umgeben ist. a representation of a UV radiation source according to the invention, which is surrounded by a liquid line.
Bei einer Vorrichtung ist zwischen einem Flüssigkeits-Vorratsbehälter 1 für Abwasser und einem Auffangbehälter 2 eine UV-Strahlungsquelle 3 angeordnet, wobei der Vorratsbehälter 1 mit einem Rührwerk 4 versehen ist. Der Vorratsbehälter 1 ist mit der Strahlungsquelle 3 über eine Verbindungsleitung 5 verbunden, in deren Verlauf sich eine Flüssigkeitspumpe 6 zur Förderung des Abwassers, ein Durchflußmesser 7 und zwei Schieber 8 und 9 zur Regulierung der Durchflußmenge befinden. Die Strahlungsquelle 3 ist mit dem Auffangbehälter 2 über eine Verbindungsleitung 10 verbunden, aus der eine Ablaßleitung 11 abzweigt, welche am Ende mit einem Schieber 12 versehen ist. Die Verbindungsleitung 5 ist über eine weitere Verbindungsleitung 13 zusätzlich mit dem Vorratsbehälter 1 verbunden, so daß eine Rückführung des Abwassers aus der Verbindungsleitung 5 in den Vorratsbehälter 1 ermöglicht wird. Zum Öffnen bzw. Schließen der Verbindungsleitung 13 weist diese einen Schieber 14 auf. Am Vorratsbehälter 1 befindet sich eine Zuführleitung 15, durch die das Abwasser in den Vorratsbehälter 1 eingebracht wird. Die Zuführleitung 15 weist einen Anschluß 16 auf, über den die Zuleitung eines Oxidationsmittels möglich ist. Der Auffangbehälter 2 besitzt eine mit einem Schieber 18 versehene Abführleitung 17, durch die das Abwasser aus dem Auffangbehälter 2 abgelassen werden kann oder zur Ausbildung eines Kreisprozesses in den Vorratsbehälter oder in eine der Verbindungsleitungen eingeleitet werden kann.In one device, a
In Figur 2 ist schematisch als UV-Strahlungsquelle ein Quarzbrenner 3 von 40 mm Außendurchmesser und 150 mm Länge dargestellt, die von einer Flüssigkeitsleitung 19 in Form einer Rohrwendel 20 umgeben ist. Dabei besteht die Flüssigkeitsleitung 19 aus Quarzglas, deren einzelne Windungen 21 dicht aneinanderliegen und mit einem geringen Steigungswinkel um die Strahlungsquelle 3 gewickelt sind. An beiden Enden der Rohrwendel 20 befinden sich Anschlüsse 22, über die die Rohrwendel beispielsweise mit den Verbindungsleitungen 5 und 10 verbindbar ist. Der Innendurchmesser der Leitung 19 kann je nach Art der zu behandelnden Flüssigkeit bei 5, 10 oder 15 mm liegen. Die Rohrwendel 20 kann eng um die Strahlungsquelle angeordnet sein. Es kann auch ein Zwischenraum für ein Kühlmedium vorgesehen sein. Die Leistung des Brenners beträgt 1,5 kW und läßt sich durch entsprechend längere Brenner erhöhen.FIG. 2 schematically shows a
Ein erfindungsgemäßes Verfahren wird mit der in Figur 1 dargestellten Vorrichtung durchgeführt. Dabei wird das Abwasser über die Zuführleitung in den Vorratsbehälter 1 eingebracht und mit Hilfe des Rührwerkes 4 gut durchmischt. Anschließend wird die UV-Strahlungsquelle in Betrieb genommen, und das Abwasser wird mit Hilfe der Pumpe 6 durch die Verbindungsleitung 5 an der Strahlungsquelle 3 vorbeigeleitet. Zum Vorbeileiten des Abwassers kann beispielsweise eine Flüssigkeitsleitung 19 verwendet werden, die in der in Figur 2 dargestellten Weise um die Strahlungsquelle 3 angeordnet ist. Das Abwasservolumen, das an der Strahlungsquelle 3 vorbeigeleitet wird, wird mit Hilfe des Durchflußmessers 7 und der Schieber 8 und 9 eingestellt. Eine ggf. auftretende Mehrleistung der Förderpumpe 6 wird über die Verbindungsleitung 13 und durch Betätigen des Schiebers 14 in den Vorratsbehälter 1 zurückgeleitet. Als Strahlungsquelle 3 wird eine rohrförmige Quecksilber-Hochdrucklampe mit einer Leistung von 1,5 kW benutzt, die von einem Quarzglasmantel umgeben ist. Über die Ablaßleitung 11 und den Schieber 12 besteht zusätzlich die Möglichkeit, während der Durchführung des Verfahrens Abwasserproben zu entnehmen. Nach der Bestrahlung wird das behandelte Abwasser in den Auffangbehälter 2 geleitet.A method according to the invention is carried out with the device shown in FIG. The wastewater is over the feed line is introduced into the
Das in Beispiel 1 verwendete Abwasser war cyanidhaltig und besaß eine Ausgangskonzentration an Cyanid von 20 mg CN-/1 Abwasser. Das Abwasser wurde auf einen ph-Wert von ≧ 10 eingestellt, um ein Entweichen von Blausäure zu vermeiden. Dieses Abwasser wurde mit verschiedenen Durchflußgeschwindigkeiten an der UV-Strahlungsquelle vorbeigeleitet und nach einmaliger Bestrahlung wurde die Cyanid-Konzentration im behandelten Abwasser gemessen. Es wurden die in der folgenden Tabelle dargestellten Ergebnisse erhalten:
Die Ergebnisse zeigen, daß bei einer nicht zu großen Durchflußgeschwindigkeit ein vollständiger Abbau des im Abwasser enthaltenen Cyanids bzw. der Cyanid-Komplexe möglich ist. Bis zu einer Durchflußgeschwindigkeit von 200 l/h ist bei der in Figur 1 dargestellten Vorrichtung eine optimale Behandlung möglich.The results show that if the flow rate is not too high, the cyanide or the cyanide complexes contained in the waste water can be completely broken down. Up to a flow rate of 200 l / h, optimal treatment is possible in the device shown in FIG.
Beispiel 2 wurde wie Beispiel 1 durchgeführt. Als Abwasser wurde ein Abwasser verwendet, das eine EDTA-Konzentration von 70 mg EDTA/l Abwasser besitzt. Zusätzlich wurde zum Abwasser über den Anschluß 16 Wasserstoffperoxid in einer Konzentration von 1 l 30%-iges H₂O₂ auf 100 l Abwasser zugegeben. Nach einmaliger Bestrahlung wurden die in der folgenden Tabelle dargestellten Ergebnisse erhalten.
Auch hier zeigt sich, daß bei nicht zu hohen Durchflußgeschwindigkeiten sehr gute Behandlungsergebnisse erhalten werden können. Auch hier liegt bei der verwendeten Vorrichtung die optimale Durchflußgeschwindigkeit unter ca. 200 l/h.Here too it can be seen that very good treatment results can be obtained if the flow rates are not too high. Here too, the optimal flow rate for the device used is less than approx. 200 l / h.
Beispiel 3 wird wie Beispiel 2 durchgeführt. Als Abwasser wird ein Abwasser, das 90 mg Methylenchlorid/l Abwasser enthält, verwendet. Über den Anschluß 16 wurde die gleiche Menge Wasserstoffperoxid wie sie in Beispiel 2 verwendet wurde, in den Vorratsbehälter zugegeben. Es wurden die folgenden Ergebnisse erhalten:
Auch bei dem in diesem Beispiel verwendeten chlorierten Kohlenwasserstoff zeigt sich, daß bei nicht zu großen Durchflußgeschwindigkeiten sehr gute Behandlungsergebnisse erhalten werden können.The chlorinated hydrocarbon used in this example also shows that very good treatment results can be obtained if the flow rates are not too high.
Für alle drei Beispiele gilt, daß bereits bei einer Bestrahlung die Konzentration an schwer abbaubaren Bestandteilen des Abwassers wesentlich reduziert werden kann. Wenn die Behandlung in einem Bestrahlungsschritt nicht ausreicht, ist es ohne weiteres möglich, die Bestrahlung mehrere Male hintereinander durchzuführen bzw. mehrere UV-Strahlungsquellen hintereinander zu schalten und das Abwasser an diesem vorbeizuführen. Auf diese Weise wird die Verweilzeit des Abwassers an der Strahlungsquelle erhöht.It applies to all three examples that the concentration of constituents of the waste water which are difficult to degrade can be significantly reduced even with irradiation. If the treatment in one irradiation step is not sufficient, it is easily possible to carry out the irradiation several times in succession or to connect several UV radiation sources in series and to guide the waste water past it. In this way, the residence time of the waste water at the radiation source is increased.
Claims (23)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4000369A DE4000369A1 (en) | 1990-01-09 | 1990-01-09 | METHOD AND DEVICE FOR WATER TREATMENT |
| DE4000369 | 1990-01-09 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0436922A2 true EP0436922A2 (en) | 1991-07-17 |
| EP0436922A3 EP0436922A3 (en) | 1991-10-09 |
Family
ID=6397747
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP19900125378 Withdrawn EP0436922A3 (en) | 1990-01-09 | 1990-12-22 | Method and apparatus for treating effluent |
Country Status (2)
| Country | Link |
|---|---|
| EP (1) | EP0436922A3 (en) |
| DE (1) | DE4000369A1 (en) |
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| DE4109872A1 (en) * | 1991-03-26 | 1992-10-01 | Univ Halle Wittenberg | Removal of oxidisable nitrogen cpds. from water - by treatment with peroxy-di:sulphate and ultraviolet light |
| DE4228460A1 (en) * | 1992-08-27 | 1994-03-03 | Wieland Edelmetalle | Treating cyanide-contg. effluent, e.g. from electroplating industry - by preheating effluent and then mixing with hydrogen peroxide. |
| US5348665A (en) * | 1991-11-22 | 1994-09-20 | Degussa Aktiengesellschaft | Method for the degradation of harmful substances in water by means of hydrogen peroxide under UV irradiation |
| AT402288B (en) * | 1994-10-12 | 1997-03-25 | Joklik Otto | DEVICE FOR PRODUCING HYGIENICALLY PERFECT ICE CUBES AND ICE SCALES |
| WO2001092459A1 (en) * | 2000-05-31 | 2001-12-06 | Brandbrew Sa | Malt beverages |
| CN101785961B (en) * | 2010-02-09 | 2012-06-27 | 浙江工业大学 | Spiral photo-reactor used for waste gas treatment and waste gas treatment process |
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| DE4126971A1 (en) * | 1991-08-14 | 1993-02-18 | Siemens Ag | METHOD AND DEVICE FOR DISPOSAL OF AN ORGANIC SUBSTANCE |
| DE4216776A1 (en) * | 1992-05-21 | 1993-11-25 | Krupp Industrietech | Detoxification of halogenated aromatic hydrocarbon cpds. using oxidant - e.g. ozone, hydrogen per:oxide or UV light causing dehalogenation and partial decomposition, e.g. for detoxifying contaminated soil or waste |
| DE4305227C1 (en) * | 1993-02-19 | 1994-08-11 | Wedeco Umwelttechnologie Wasser Boden Luft Gmbh | Device for disinfecting flowing media |
| DE4317939C2 (en) * | 1993-04-27 | 1995-09-28 | Darius Jung | Device for optimizing the intensity of the radiation aimed at liquid waste and waste water to be irradiated |
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| US5439595A (en) * | 1993-08-25 | 1995-08-08 | Downey, Jr.; Wayne F. | Water decontamination method using peroxide photolysis ionizer |
| US5958247A (en) * | 1994-03-28 | 1999-09-28 | Siemens Aktiengesellschaft | Method for disposing of a solution containing an organic acid |
| DE19543503C2 (en) * | 1995-11-22 | 2000-01-05 | Nukem Gmbh | Method and device for irradiating liquids with high-energy radiation and use of the device |
| DE19624015A1 (en) * | 1996-06-15 | 1997-12-18 | Boehringer Mannheim Gmbh | Sample analyser with unit to reduce halogenated compounds in waste |
| DE29809867U1 (en) | 1998-06-04 | 1998-09-24 | Büttner, Klaus, Dipl.-Ing., 25336 Klein Nordende | UV lamp for hemodialysis |
| DE10046959B4 (en) * | 2000-09-18 | 2008-01-31 | Schuldes, Wolfgang, Dr.-Ing. | Process for the complete removal of pollutants from highly polluted industrial sludges and waste water and apparatus for carrying out the process |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4109872A1 (en) * | 1991-03-26 | 1992-10-01 | Univ Halle Wittenberg | Removal of oxidisable nitrogen cpds. from water - by treatment with peroxy-di:sulphate and ultraviolet light |
| US5348665A (en) * | 1991-11-22 | 1994-09-20 | Degussa Aktiengesellschaft | Method for the degradation of harmful substances in water by means of hydrogen peroxide under UV irradiation |
| DE4228460A1 (en) * | 1992-08-27 | 1994-03-03 | Wieland Edelmetalle | Treating cyanide-contg. effluent, e.g. from electroplating industry - by preheating effluent and then mixing with hydrogen peroxide. |
| AT402288B (en) * | 1994-10-12 | 1997-03-25 | Joklik Otto | DEVICE FOR PRODUCING HYGIENICALLY PERFECT ICE CUBES AND ICE SCALES |
| WO2001092459A1 (en) * | 2000-05-31 | 2001-12-06 | Brandbrew Sa | Malt beverages |
| GB2378449A (en) * | 2000-05-31 | 2003-02-12 | Brandbrew Sa | Malt beverages |
| GB2378449B (en) * | 2000-05-31 | 2004-10-06 | Brandbrew Sa | Malt beverages |
| CN101785961B (en) * | 2010-02-09 | 2012-06-27 | 浙江工业大学 | Spiral photo-reactor used for waste gas treatment and waste gas treatment process |
Also Published As
| Publication number | Publication date |
|---|---|
| DE4000369A1 (en) | 1991-07-11 |
| EP0436922A3 (en) | 1991-10-09 |
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